US1835426A

US1835426A - Destructive hydrogenation of carbonaceous materials

Info

Publication number: US1835426A
Application number: US302639A
Authority: US
Inventors: Pier Mathias
Original assignee: Standard IG Co
Current assignee: Standard IG Co
Priority date: 1927-10-27
Filing date: 1928-08-28
Publication date: 1931-12-08
Anticipated expiration: 1948-12-08

Description

Dec. 8, 1931. M. PIER 1,835,426

DESTRUCTIVE HYDROGENATION OF CARBONACEOUS MATERIALS Original Filed Oct. 27, 1927 E R w q is a 10 l T 12 INVENTOR BYZLis ATTORNEYS Patented Dec. 8, 1931 UNITED STATES PATENT OFFICE MATHIAS PIER, 0F HEIDELBERG, GERMANY, ASSIGNOR, BY MESNE ASSIGNMENTS, TO

STANDARQ-I. G. COMPANY, OF LINDEN, NEW JERSEY, A CORPORATION OF DELA- WARE DE-STR'O'CTIVE HYDROGENAYTION or CARBONACEOUS MATERIALS Original application filed October 27, 1927, Serial No. 229,084, and in Germany August 7, 1926. Divided and this application filed August 28, 1928. Serial No. 302,639.

This application is a divisional application and relates to subject-matter which has been divided out from my copending appli-' cation for Patent Ser. No. 229,084 filed Octoher 27th, 1927.

The'present invention relates to the manufacture of valuable hydrocarbons and deriva-' tives by the destructive hydrogenation of car ment of the said materials with hydrogen or' gases containing or giving-oil hydrogen, at elevated temperatures and under a high pressure of atmospheres or more of the hydrogenating gas, in the absence or presence of catalysts.

I have now found that if initial materials are employed, which are free from sulfur or its compounds the reaction vessel, and preferably also the other parts of the apparatus which come into contact with thehot organic reacting material'may be constructed of or lined with copper or alloys thereof. Otherwise spongy sulfurous masses are formed which lead to rapid corrosion of the apparatus and which moreover cause deposi-' tion of carbon and formation of methane. Accordingly care must be taken that the reaction vessel including the catalyst, the walls of the vessel and, if such be arranged therein, the heating devices. and preferably also the other hot parts of the apparatus such as the pipings, heat regeneratorsand the like which come into contact with the organic reacting materials, are free from such substances as would cause the said obnoxious by-reactions. It is also necessary to prevent the initial materials and especially the gases from conveying obnoxious substances into the reaction vessel or the other hot parts of the apparatus.

The apparatus may also in part be constructed of or coated with alloys containing cobalt, molybdenum, tungsten, vanadium or manganese, or several of these elements and in addition thereto, if desired, a considerable percentage of nickel, in particular highly'alloyed steels containing the said elements or with silver or alloys thereof.

These parts of the apparatus which come into contact with hot organic materials may also be provided with a content in certam metalloids such as boron, arsenic, antimony, silicon, bismuth, phosphorus, selenium and the like. These metalloids may be alloyed with the metals, or they may be incorporated only with the surfaces thereof, for example by the action of compounds of the said metalloids on the surfaces of the apparatus. Also by this means the formation of methane and the separation of carbon are considerably reduced. l

Such metals and alloys are also very suitable for construction of parts of the appararatus in which the boundaries of the crystal grains are substantially free from impurities as can be determined by microscopic examination. By such absence of impurities a stable crystal structure is obtained, as a consequence of which the material is not attacked even when the apparatus is subjected to a very severe treatment for a very long period. In some cases, such substantially pure metals or alloys are attacked but such attack takes place only superficially, and accordingly, when the superficial layer which has been exposed to attack, peels off, a smooth surface free from pores is formed again which does not give rise to any obnoxious ad ditions, whereas with the usual metals entire structure would be loosened and accordingly thematerial would become porous. In the case of the said superficial attack of the metals or alloys free from impurities, the surface thereof may be kept clean and suitable for working in any suitable way, for

and preferably smooth surface. For this purpose the catalysts may be constructed in any suitable manner for example they may be sheets or wires which may be heated to the temperature of the reaction for example by electric resistance heating. Catalysts of this kind are distinguished by their excellent stability in continued use. In order to keep the catalytically acting surfaces clean and smooth, it is advantageous to maintain a high speed of the reacting materials or gases so that a great relative movement between the catalytic surfaces and the reacting materials is established. This may be furthered by mechanically setting the catalysts into movement.

The initial materials may be employed in a solid or liquid and preferably in a finely divided, for example atomized, state, or in the form of vapor. It is advantageous to work with the hydrogenating gas in a circulatory course and to provide an intimate contact of the said hydrogenating gas with the materials to be treated for example by employing the latter in the form of thin layers or by stirring, atomizing and the like.

The process according to the present invention is preferably carried out with a large excess of hydrogenating gas and with streaming gases, the reaction vessel, and preferably also the other parts of the apparatus which come into contact with the hot organic reacting material being kept free from such substances as would give rise under the conditions of Working to the formation of methane and deposition of carbon.

The process according to this invention is especially suitable for the production of valuableliquid fuels such as benzine, heavy oils for Diesel engines and the like, for the production of benzene and its' homologues and also in'the manufacture of valuable lubrieants, solvents and the like.

The present invention will be further described with reference tothe accompanying drawing representing in a. diagrammatic manner a vertical section of an apparatus especially suitable for carrying out this invention which, however, is not restricted thereto.

Referring to the drawing in detail numeral 11 denotes a hydrogenating vessel, the wall 1 of which is coated with a lining 12 consisting of copper. The initial material, free from sulphur, is introduced at 7 into the heat regenerator 3 and is heated in coil 8 surrounding tubes 5 through which tubes hot materials issuing from the destructive hydrogenation are flowing. The preheated materials then pass through pipe 9 and are heated to the reaction temperature in the heating coil 13; they enter the hydrogen'ating vessel at 10.

What I claim is:

1. In the destructive hydrogenation of carbonaceous materials at pressures of at least 50 atmospheres of hydrogenating gas in apparatus the inner surfaces of which are constructed wholly or in part of copper or alloys thereof the step which com rises excluding sulphur and its compounds rom the material under treatment.

2. In the destructive hydrogenation of carbonaceous materials at pressures of at least 50 atmospheres of hydrogenating gas in apparatus the inner surfaces of which are constructed wholly or in part of copper or alloys thereof the step which comprises excluding sulphur and its compounds from the ma terial under treatment and operating in streaming gases with a large excess of the hydrogenatmg gas.

3. In the destructive hydrogenation of carbonaceous materials at pressures of at least 50 atmospheres of hydrogenating gas in apparatus, the inner surfaces of which are constructed at least in part of copper or alloys thereof, the step of operating with initial materials which are free from sulphur and its compounds.

4. In the destructive hydrogenation of carbonaceous materials at pressures of at least 50 atmospheres of hydrogenating gas in apparatus the inner surfaces of which are constructed at least in part of copper or alloys thereof, the step of operating with initial materials which are free from sulphurand its compounds and operating with a large excess of streaming hydrogenating gas.

In testimony whereof, I afiix my signature.

' MATHIAS PIER.